Wiashafek -on -the-ehine



Patented Apr. 21, 1931 umrso STATES PATENT OFFICE FRITZ GUE'NTHER, FRITZ TELLEB, CARL IMMERHEISER, AND BODO ZSCHIMMEE, OF LUD- WIGSEAFEN-ON-TEIE-RHINE, GERMANY, ASSIGNORS TO I. G. IIQAIBJBENJIIHMJ'S'LCBIEv .AKTIENGESELLSGHAFT, OF FBANKFORT-ON-THE-MAIN, GERMANY, A CORPORATION OF GERMANY I EMULs rYms AGENT No Drawing. Original application filed September 13, 1926, Serial No. 185,284, and in Germany April 28, 1928. Divided and this application filed October 24, 1928. Serial No. 314,840.

The present application has been divided out from the application Ser. No. 135,294, filed September 13, 1926.

Emulsions of liquid or solid materials difficultly soluble or insoluble in water or not miscible therewith are usually prepared with the aid of soap or substances possessing similar properties, such as Turkey red oil, organic sulfonic acids and the like; solid materials are emulsified in the form of a melt or of a solution in a suitable solvent. In many cases, however, a satisfactory result .is not obtained b this method. For example it is not possib e to form a stable emulsion of olive oil in water with the ai'd'of soap or sulfonic acids of soap-like character.

. We have now found that oils, fats, waxes,

hydrocarbons, alcohols, ketones, esters, and other materials insoluble or difiicultly soluble in water or not miscible therewith, whether solid or liquid, can be converted into emulsions which are very stable even when diluted with water and in many cases even in the presence of acids by employing a soap or a substance having soap-like properties in conjunction with a protective colloid such as glue, gelatine, casein, agar-agar, dimethyl- .cellulose and the like, or with water-soluble gums such as gum arabic or similar materials.

'As examples of substances having soap-like properties applicable according to the presout invention we mention grain or soft or other soaps, Turkey red oil, saponines, salts of cholic acid, sulfite cellulose waste liquor, tri-oxyethylamine, alkylated aromatic sulfonic acids, especially those of the naphtha- ,lene series and the like. 1

Instead of adding the said ingredients 0 the two groups successively in the course of the emulsifying process, the said soap-like and the protective colloids may also be mixed beforehand; thereby readily storable and marketable emulsifying preparations are obtained which are at once ready for use.

'We have further found that such mixtures can be advantageously employed for the preparation of mineral or artificial materials such as inorganicv or organic colors, soot, sulfur, blanc fixe and the like, in a finely subpared by initimately mixing 95 parts of divided state, for which purpose the said mixtures are added to the liquid in which the said materials are prepared or by adding them in the course of the milling process. By this means the materials are obtained in a state of such a fine dispersion as cannot be produced by the methods hitherto in use; by reason of the fine subdivision for example coloring matters and pigment colors possess a very great coloring and covering power.

The following examples will further illustrate how our invention may be carried out in practice, but the invention is not limited to these examples. The parts are by weight, unless otherwise stated.

Example 1 on a hot water bath while stirring or it may be evaporated to dryness in vacuo and finely powdered.

By introducing, while stirring, 16 parts of olive oil into one part of the powdered emulsifying agent mentioned above dissolved in 4 parts of water, a salve-like mass is obtained after some time which bystirring with water is converted into a thin liquid of milk-like appearance. a

. The emulsifying agent can. also be ly. powdered glue with 35 parts of isopr'opylnaphthalene sulfonic acid sodium salt in the solid state; 1 part of this mixture dissolved in! parts of water is capable of emulsifying 15 or more parts of olive oil.

Instead of the isopropyl-naphthalene sul- 'fonic acid sodium salt, other substances of soap properties, for example 40 parts of grain soap may be employed.

. Example 2 ii?" I cent solution are stirred with about 4 parts pf bone glue dissolved in about 9 parts of water. This mixture is suitable for example for emulsi ing about parts of olive oil.

sample 3 ing examples Turkey red oil, saponines an salts of sulfonic acids other than isopropyl-naphthalene sulfonic acid sodim salt may be employed as substances having soap-like properties. The glue may be 1:1) aced for example by gelatin or by gum are 10.

Instead of olive oil, other oils such as cas tor oil, linseed oil, mineral oils, oleic acid and the likevcan be emulsified Example 4 300 parts, by volume, of a 20 per cent solution of glue are mixed with a solution of arts'oi isopropyl-naphthalene sulfonic aci sodium salt in 150 parts, by volume, of

I and the like may be employed. The isopropyl-naphthalene sulfomcacid sodium salt may be replaced by about the same quantity of the sodlum salt of butyl-naphthalene sul- I fonic acid, N-diamyl-naphthylamine sulfonic acid or dibutyl-sulfanilic acid.

Ewample 5 20 parts of the sodium salt of a resin sulionic acid obtainable by sulfonating rosin, are dissolved in parts of water and mixed with a solution of: 40 parts of glue in 120 parts of water. The mixture is concentrated on a water bath at a low temperature, evaporated to dryness in vacuo and powdered.

1 part of this emulsifying agent dissolved in 3 parts of water is capable of emulsifying 15 parts of olive oil.

Ewample 6' 100 parts of the yellow pigment color obtamed from diazotized 5-nitro4-toluidine and aceto-acetic-anilide are intimately 3 1. The process of dispersing ground in the dry state with 15 parts of powdered glue and 3 parts of benzyl-aniline sulfonic acid sodium salt. The resulting coloring matter is Very finely divided in comparison with the initial material. It forms highly dispersed suspensionswhen made into a paste with water, which suspensions may be employed with advantage for example for coloring paper pulp, for-the production of paste colors for wall papers and the like.

In a similar manner, other substances for example casein, or m arabic may be employed instead of g us. The benzyl-aniline sulfonic acid sodium salt may be replaced by saponines, cholic acid'salts, sulfite cellulose waste liquor, salts of alk lated naphthalene sulfonic acids and the lil e. The uantities of the ingredients employed may varied within wide limits.

Instead of starting from the powdery dyestuff, it is also possible to employ an aqueous paste of the coloring matters, to mix same with the dispersing agents or their solutions, whereupon the mass is dried and Grindin may be dispensed with, if t e drying is.e ected so as to obtain directly a dry powdery product.

Ewample '7 15-parts-of beta-naphthol are dissolved in 500 parts'of water by addin 13 parts of caustic soda lye of 40 degrees aum and 10 parts of soda ash. A mixture of 3 arts of glue and 1 part of tri-oxyethyl-amine, dissolved in 40 parts of water, is added to the solution, whereupon a solution of the diazo compound of 13.8 parts of para-nitroaniline is caused to run into the mixture. The coloring matter separates out in a so finely divided state as cannot be obtained b ment of glue or tri-oxyethy -amine a one. Instead of the tri-oxyethyl-amine for example saponines, Turkey red oil or naphthaline sullfonig acid sodiuin sailts spbstituted in t e nuc eus y isopropy or at groups may be employed; the glue may b replaced by starch, water-soluble gums and the like.

The processes described in the above Examples 6 and 7 may also be carried out in the presence of substrates such as are usual in-the industry of color lakes.

Example 300 arts of water are mixed with an a neous so ution of 2.5 parts of cellulose dimet yl ether and 2.5 parts of isopropyl-naphthalene sulfonic acid sodium salt. 80 parts of olein are then caused to run in while continuously stirring. A homogeneous emulsion is ob tained which may be employed for example v 125 for oiling wool.

What we claim is:

, materials which comprises'treating the -material with a hydroxy alk l-amine in conjunction with a protective collziid.

the em loy-' 2. The process of prodncin fineliy divided solid materials characterize by mixing a I suspension of a dyestuif with tri-hydroxyethyl-amine and a protective colloid.

5. A composition of matter comprisin trihydroxyethyl-amine and a protectlve co oid. 6. A composition of matter comprising a coloring matter, tri-hydroxyethyl-amine and a rotective colloid.

, A composition of matter comprising an organic dyestufi, tri-hydroxyethyl-amine and a protectlve colloid.

8. A composition of matter comprising a lake of an organic dyestufi, tri-hydroxyethylamme and a protective colloid.

In testimony whereof, weafiix our signatures.

FRITZ GUENTHER. I FRITZ TELLER. A CARL IMMERHEISER.

. BODO ZSOR 

